Chlorine disposal

If the hydrogen chloride cannot be sold, it must be disposed of somehow. Alternatively, it could be converted back to chlorine via the reaction... 

In early designs, the reaction heat typically was removed by cooling water. Crude dichloroethane was withdrawn from the reactor as a liquid, acid-washed to remove ferric chloride, then neutralized with dilute caustic, and purified by distillation. The material used for separation of the ferric chloride can be recycled up to a point, but a purge must be done. This creates waste streams contaminated with chlorinated hydrocarbons which must be treated prior to disposal. 

Compatibihty of acetone with other materials should be carefliUy considered, especially in disposal of wastes. It reacts with chlorinating substances to form toxic chloroketones, and potentially explosively with some peroxy compounds and a number of oxidizing mixtures. Mixed with chloroform, acetone will react violently in the presence of bases. Other incompatibilities ate Hsted in the Sax handbook (53). 

Disposal. Moderate amounts of chlorine ttifluoride or other halogen fluorides may be destroyed by burning with a fuel such as natural gas, hydrogen, or propane. The resulting fumes may be vented to water or caustic scmbbers. Alternatively, they can be diluted with an inert gas and scmbbed in a caustic solution. Further information on disposal of halogen fluorides is available (115—118). 

Plant investment and maintenance costs are relatively high for a new iodine plant in the United States or in Japan because of the deep weUs required for brine production and disposal as weU as the corrosive nature of the plant streams. The principal materials cost is for chlorine and for sulfur dioxide, although in the United States the additives used for the brines, such as scale inhibitors and bactericides, also have a considerable influence on costs. 

Regulations. In order to decrease the amount of anthropogenic release of mercury in the United States, the EPA has limited both use and disposal of mercury. In 1992, the EPA banned land disposal of high mercury content wastes generated from the electrolytic production of chlorine—caustic soda (14), accompanied by a one-year variance owing to a lack of available waste treatment faciUties in the United States. A thermal treatment process meeting EPA standards for these wastes was developed by 1993. The use of mercury and mercury compounds as biocides in agricultural products and paints has also been banned by the EPA. 

TSCA also addresses the problem of polychlorinated biphenyls (PCBs) and chlorinated fluorocarbons (CECs). EPA has developed regulations on the cleanup, handling, and disposal of PCBs. The manufacture and use of CECs has been banned for all but essential uses, in accordance with the Montreal Agreement, an international treaty on worldwide use of CECs. 

Chlorinated by-products of ethylene oxychlorination typically include 1,1,2-trichloroethane chloral [75-87-6] (trichloroacetaldehyde) trichloroethylene [7901-6]-, 1,1-dichloroethane cis- and /n j -l,2-dichloroethylenes [156-59-2 and 156-60-5]-, 1,1-dichloroethylene [75-35-4] (vinyhdene chloride) 2-chloroethanol [107-07-3]-, ethyl chloride vinyl chloride mono-, di-, tri-, and tetrachloromethanes (methyl chloride [74-87-3], methylene chloride [75-09-2], chloroform, and carbon tetrachloride [56-23-5])-, and higher boiling compounds. The production of these compounds should be minimized to lower raw material costs, lessen the task of EDC purification, prevent fouling in the pyrolysis reactor, and minimize by-product handling and disposal. Of particular concern is chloral, because it polymerizes in the presence of strong acids. Chloral must be removed to prevent the formation of soflds which can foul and clog operating lines and controls (78). 

Although there are minor differences in the HCl—vinyl chloride recovery section from one vinyl chloride producer to another, in general, the quench column effluent is distilled to remove first HCl and then vinyl chloride (see Eig. 2). The vinyl chloride is usually further treated to produce specification product, recovered HCl is sent to the oxychlorination process, and unconverted EDC is purified for removal of light and heavy ends before it is recycled to the cracking furnace. The light and heavy ends are either further processed, disposed of by incineration or other methods, or completely recycled by catalytic oxidation with heat recovery followed by chlorine recovery as EDC (76). 

By-Product Disposal. By-product disposal from vinyl chloride manufacturing plants is compHcated by the need to process a variety of gaseous, organic Hquid, aqueous, and soHd streams, while ensuring that no chlorinated organic compounds are inadvertendy released. Each class of by-product streams poses its own treatment and disposal challenges. 

Chlorine. Nearly all chlorine compounds are readily soluble in water. As a result, the major reservoir for this element in Figure 1 is the ocean (5). Chloride, as noted earHer, is naturally present at low levels in rain and snow, especially over and near the oceans. Widespread increases in chloride concentration in mnoff in much of the United States can be attributed to the extensive use of sodium chloride and calcium chloride for deicing of streets and highways. Ref. 19 points out the importance of the increased use of deicing salt as a cause of increased chloride concentrations in streams of the northeastern United States and the role of this factor in the chloride trends in Lake Ontario. Increases in chloride concentration also can occur as a result of disposal of sewage, oil field brines, and various kinds of industrial waste. Thus, chloride concentration trends also can be considered as an index of the alternation of streamwater chemistry by human development in the industrialized sections of the world. Although chlorine is an essential element for animal nutrition, it is of less importance for other life forms. 

Microstrainers. Microstrainers are rotating steel screens with extremely fine stainless steel mesh (85—170 perforations per square centimeter (13—26/in. )). The flowing Hquid enters the open end of the dmm and passes through the mesh to the effluent end. The mesh traps soHd impurities and rotates with the dmm. A wash-water spray washes the trapped soHds into a hopper for final disposal. The mesh is washed with filtered effluent discharged from jets fitted into the dmm and then exposed to uv radiation to inhibit microbial growth. The mesh is washed with chlorine water at intervals of 7 to 28 days in order to control slime growth removal efficiencies are 30—55% of the appHed BOD and 40—60% of suspended soHds. 

Environmental problems associated with PCBs are the result of a number of factors. Several open uses of PCBs have resulted in thein direct introduction into the environment, eg, organic diluents careless PCB disposal practices have resulted in significant releases into aquatic and marine ecosystems higher chlorinated PCBs are very stable in thein persistence in different environmental matrices and by a variety of processes (Fig. 1) PCBs are transported throughout the global ecosystem and preferentiaHy bioconcentrate in higher trophic levels of the food chain. 

Yields of propylene chlorohydrin range from 87—90% with dichloropropane yields of 6—9%. The dichloropropane is not only a yield loss but also represents a disposal problem as few uses are known for this material. Since almost all the propylene chlorohydrin is dehydrochlorinated to propylene oxide with lime or sodium hydroxide, none of the chlorine appears in the final product. Instead, it ends up as dilute calcium or sodium chloride solutions, which usually contain small amounts of propylene glycol and other organic compounds that can present significant disposal problems. 

There have been a number of cell designs tested for this reaction. Undivided cells using sodium bromide electrolyte have been tried (see, for example. Ref. 29). These have had electrode shapes for in-ceU propylene absorption into the electrolyte. The chief advantages of the electrochemical route to propylene oxide are elimination of the need for chlorine and lime, as well as avoidance of calcium chloride disposal (see Calcium compounds, calcium CHLORIDE Lime and limestone). An indirect electrochemical approach meeting these same objectives employs the chlorine produced at the anode of a membrane cell for preparing the propylene chlorohydrin external to the electrolysis system. The caustic made at the cathode is used to convert the chlorohydrin to propylene oxide, reforming a NaCl solution which is recycled. Attractive economics are claimed for this combined chlor-alkali electrolysis and propylene oxide manufacture (135). 

Residuals Produced Typical residuals resulting from oxidation are partial oxidation products (e.g., chlorinated organics) and inorganic salts (e.g., NaCl, Mn02). Additional treatment may be required to permit disposal. 

Corrective Action Application At a hazardous waste treatment storage and disposal facility in Washington State, a cyanide-bearing waste required treatment. The influent waste stream contained 15 percent cyanide. Electrolytic oxidation was used to reduce the cyanide concentration to less than 5 percent. Alkaline chlorination was used to further reduce the cyanide concentration to 50 mg/1 (the cleanup objective). The electrolytic process was used as a first stage treatment because the heat of reaction, using alkaline chlorination to treat the concentrated cyanide waste, would be so great that it would melt the reactor tank. 

Case 2 - The Hyde Park Landfill site, located in an industrial complex in the extreme northwest corner of Niagara, New York, was used from 1953 to 1975 as a disposal site for an estimated 80,000 tons of chemical waste, including chlorinated hydrocarbons. A compacted clay cover was installed in 1978 over the landfill and a tile leachate collection system was installed in 1979. Hazardous compounds such as ortho-, meta- and para-chlorobenzoic acid toluene ortho- and meta-chlorotoluene 3,4-dichlorotoluene and 2,6-dichlorotoluene were detected in the leachate (Irvine et al., 1984). Since 1979, the existing leachate treatment system has used activated carbon as the technology for removing organic carbon. Although... 

Precipitation is nonselective in that compounds other than those targeted may be removed. Both precipitation and flocculation are nondestructive and generate a large volume of sludge which must be disposed of. Coagulation, flocculation, sedimentation, and filtration, are typically followed by chlorination in municipal wastewater treatment processes. 

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